CN104525206A - Porous ozone catalyst for removing COD from waste water and preparation method thereof - Google Patents
Porous ozone catalyst for removing COD from waste water and preparation method thereof Download PDFInfo
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- CN104525206A CN104525206A CN201410726364.8A CN201410726364A CN104525206A CN 104525206 A CN104525206 A CN 104525206A CN 201410726364 A CN201410726364 A CN 201410726364A CN 104525206 A CN104525206 A CN 104525206A
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Abstract
The invention discloses a preparation method for a porous ozone catalyst used for removing COD from waste water. The porous ozone catalyst is prepared from one or more metal catalytic oxides, an inorganic material and an organic material through mixing, molding, drying and sintering processes. The prepared porous ozone catalyst provided by the invention is applied to organic molecules in waste water containing organic waste like COD and has the characteristics of high selectivity and highly-efficient ozone oxidation performance; moreover, the catalyst has the advantages of small usage amount and long service life, can be widely applied to ozone oxidation treatment of COD in industrial and agricultural waste water or sanitary sewage and waste water, greatly improves ozone oxidation efficiency, and enables COD in treated waste water to be reduced to 30mg/L, meeting national first-grade discharge standard.
Description
Technical field
The present invention relates to a kind of porous ozone catalyst removing COD in waste water and preparation method thereof.
Background technology
At present, the process of industrialization in the world creates a large amount of industry containing COD, agricultural, fishery and life liquid waste.Conventional biochemical treatment is difficult to discharge standard COD being dropped to current national regulation.Ozone oxidation is often used to reluctant for biochemistry COD to reduce further, but the limited efficacy of ozone oxidation COD and operating cost is high.
In order to overcome these problems, some ozone oxidation catalysts have been used to improve the efficiency of ozone oxidation, but usually DeGrain.
Summary of the invention
The present invention, in order to solve the above-mentioned deficiency of prior art, proposes a kind of preparation method removing the porous ozone catalyst of COD in waste water.
In order to solve the problems of the technologies described above, the present invention is by the following technical solutions: a kind of preparation method removing the porous ozone catalyst of COD in waste water, its porous ozone catalyst is made up of the porous material matrix that aperture is controlled, and described porous material matrix is prepared from through the following step by metal oxide, inorganic material, organic material:
1) take a certain amount of metal oxide, inorganic material, organic material insert in ball grinder, add water and dispersant, carry out mixing and ball milling slurrying;
2) again by above-mentioned slurry by rolling slurry, pinch and to rub or this material is made mud powder by spraying dry;
3) the mud powder of gained is extruded balling-up or mechanical rolling balling by extruder;
4) spheroidal material of gained is put into baking oven inner drying, be dried to moisture lower than 0.8%;
5) finally dried spheroidal material is put into electric furnace to sinter, thus obtained required product.
Wherein, further, described metal oxide is Al
2o
3, SnO, Sb
2o
3, Fe
2o
3, FeO, CuO, CuO, TiO
2, NiO, MnO, Mn
2o
3, V
2o
5, MgO, Cr
2o
3in one or more mixture.
Further, the percentage by weight that described metal oxide accounts for total amount is 2-45%.
Further, described inorganic material is one or more the mixture in potassic feldspar, bentonite, silica flour, calcite, talcum powder, graphite powder, sodium phosphate trimer, coal dust, bauxite, organic polymer material.
Further, described organic compound is starch, carbon dust or coal.
Further, in described step 5), the temperature of electric furnace controls at 500-1350 DEG C, and sinters in reduction or oxidizing atmosphere.
Be 0.1-300mm according to the particle diameter of the porous ozone catalyst prepared by preparation method above, porosity is 20-80%, and aperture is 1nm-3000 nm, and specific area is 0.1-1000 ㎡/g.
Compared with prior art, beneficial effect of the present invention is: of the present invention be applied to remove the porous ozone catalyst of COD in waste water have to the high selectivity of COD and ozone oxidation efficiency high, the chemical stability of catalyst own is good, mechanical strength is high, and there is the feature of long service life, Industrial Wastewater Treatment can be widely used in, mine smelts, plating, electronics is produced, in printing and dyeing garment making industry, also can be applicable to municipal sewage, river, the improvement of lake and other underground water, be specially adapted to carry out advanced treating to the waste water lower containing COD concentration, make the COD in process water can reach national grade one discharge standard or 30mg/L.
Detailed description of the invention
Below invention is described in detail.
Embodiment 1:
The preparation of porous ozone catalyst: take cupric oxide 0.6 kilogram, potassic feldspar 1 kilogram, bentonite 50 kilograms, silica flour 2 kilograms, 0.5 kilogram, calcite, talcum powder 0.5 kilogram, graphite powder 2.5 kilograms, add water again, ball, dispersant, dispersant is sodium phosphate trimer, their proportionings are material: water: ball: dispersant=1: 0.8: 2: 0.003, then put into together inside ball grinder and carry out ball milling 18 hours; The slurry that ball milling completes is crossed 300 eye mesh screens, pours in stainless steel disc, then put into baking oven together and dry; The mud powder that drying completes is carried out shaping balling-up by extruder, ball is put into oven drying, dry moisture, lower than 0.8%, finally uses electric furnace to burn till;
Embodiment 2:
The preparation of porous ozone catalyst: take Fe
2o
31 kilogram, 100 grams, tin oxide, cobalt oxide 100 grams, cupric oxide 100 grams, nickel oxide 200 grams, manganese oxide 200 grams, potassic feldspar 3 kilograms, bentonite 5 kilograms, silica flour 3 kilograms, 1.5 kilograms, calcite, graphite powder 3.5 kilograms, and then add water, ball, their proportionings are material: water: ball=1: 0.8: 2, put into together inside ball grinder and carry out ball milling 18 hours; The slurry that ball milling completes is crossed 300 eye mesh screens, pours in stainless steel disc, then put into baking oven together and dry; The mud powder that drying is completed, by mechanical rolling balling, puts into oven drying ball, and dry moisture, lower than 0.8%, finally uses electric furnace to burn till.Thus synthesizing porous ozone catalytic agent material.The specific surface of this porous ozone catalyst is 210m2/g, and average pore size is 20nm.
Embodiment 3:
Experiment wastewater: percolate concentrates liquid 1
Experimental provision: oxygen tank, ozone generator, glass column, water pump.
Catalysis material: the catalysis material of 200g embodiment 1
Experimental procedure:
1) get 1300ml concentrate dress post, open oxygen valve, control air pressure is 0.2MPa.
2) open ozone generator switch, control flow is 0.5L.min, and electric current is 0.2A.
3) open water pump, open backflow.
4) sample was got every one hour
Experimental result is as following table 1:
Table 1
| Time/h | 0 | 1 | 2 | 3 | 4 | 5 |
| Catalysis material+ozone | 4780 | 1350 | 1260 | 980 | 1050 | 984 |
| Simple ozone | 4972 | 3778 | 2860 | 1611 | 1560 | 1483 |
Reach a conclusion: the COD of oxidation rate catalysis material of the present invention concentrates to(for) percolate was 2.87 times of simple ozone oxidation speed at the first hour.
Embodiment 4:
Experiment wastewater: percolate concentrates liquid 2
Experimental provision: oxygen tank, ozone generator, glass column, water pump.
Catalysis material: the catalysis material of 200g embodiment 2
Experimental procedure:
1) get 1300ml concentrate dress post, open oxygen valve, control air pressure is 0.2Mpa;
2) open ozone generator switch, control flow is 0.5L.min, and electric current is 0.2A;
3) open water pump, open backflow;
4) sample was got every one hour.
Experimental result is as following table 2:
Table 2
| Time/h | 0 | 1 | 2 | 3 | 4 | 5 |
| Catalysis material+ozone | 1500 | 761 | 556 | 347 | 170 | 153 |
| Simple ozone | 1530 | 1028 | 750 | 361 | 181 | 156 |
Reach a conclusion: the COD of oxidation rate catalysis material of the present invention concentrates to(for) percolate was 1.47 times of simple ozone oxidation speed at the first hour.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.
Claims (7)
1. remove the preparation method of the porous ozone catalyst of COD in waste water for one kind, its porous ozone catalyst is made up of the porous material matrix that aperture is controlled, it is characterized in that: described porous material matrix is prepared from through the following step by metal oxide, inorganic material, organic material:
1) take a certain amount of metal oxide, inorganic material, organic material insert in ball grinder, add water and dispersant, carry out mixing and ball milling slurrying;
2) again by above-mentioned slurry by rolling slurry, pinch and to rub or this material is made mud powder by spraying dry;
3) the mud powder of gained is extruded balling-up or mechanical rolling balling by extruder;
4) spheroidal material of gained is put into baking oven inner drying, be dried to moisture lower than 0.8%;
5) finally dried spheroidal material is put into electric furnace to sinter, thus obtained required product.
2. the preparation method removing the porous ozone catalyst of COD in waste water as claimed in claim 1, is characterized in that: described metal oxide is Al
2o
3, SnO, Sb
2o
3, Fe
2o
3, FeO, CuO, CuO, TiO
2, NiO, MnO, Mn
2o
3, V
2o
5, MgO, Cr
2o
3in one or more mixture.
3. the preparation method removing the porous ozone catalyst of COD in waste water as claimed in claim 2, is characterized in that: the percentage by weight that described metal oxide accounts for total amount is 2-45%.
4. the preparation method removing the porous ozone catalyst of COD in waste water as claimed in claim 1, is characterized in that: described inorganic material is one or more the mixture in potassic feldspar, bentonite, silica flour, calcite, talcum powder, graphite powder, sodium phosphate trimer, coal dust, bauxite, organic polymer material.
5. the preparation method removing the porous ozone catalyst of COD in waste water as claimed in claim 1, is characterized in that: described organic compound is starch, carbon dust or coal.
6. the preparation method removing the porous ozone catalyst of COD in waste water as claimed in claim 1, it is characterized in that: in described step 5), the temperature of electric furnace controls at 500-1350 DEG C, and sinters in reduction or oxidizing atmosphere.
7. the porous ozone catalyst made by the arbitrary described preparation method of claim 1-6, it is characterized in that: the particle diameter of described obtained porous ozone catalyst is 0.1-300mm, porosity is 20-80%, and aperture is 1nm-3000 nm, and specific area is 0.1-1000 ㎡/g.
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| CN104923238A (en) * | 2015-05-25 | 2015-09-23 | 北京铸盟科技有限公司 | Oxidization catalyst used for advanced oxidation, preparation method thereof and application thereof |
| CN105396549A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Preparation method for adsorption material used for treating dye waste water |
| CN105498754A (en) * | 2015-12-23 | 2016-04-20 | 北京碧水源膜科技有限公司 | Catalyst for catalytic oxidation of ozone and preparation method of catalyst |
| CN105838828A (en) * | 2016-05-26 | 2016-08-10 | 许婷 | Leather working treating agent and preparation method thereof |
| CN106040252A (en) * | 2016-05-26 | 2016-10-26 | 格丰环保科技有限公司 | Method for preparing ozone oxidation catalyst |
| CN106799226A (en) * | 2017-01-05 | 2017-06-06 | 杭州绿色环保技术开发有限公司 | A kind of catalyst of ozone oxidation organic matter and preparation method thereof |
| CN106902812A (en) * | 2017-03-14 | 2017-06-30 | 南京大学 | A kind of preparation method of the loaded catalyst for heterogeneous catalysis ozonisation |
| CN108585371A (en) * | 2018-05-18 | 2018-09-28 | 河南海天水务工程有限公司 | A kind of sewerage integrated treatment process of drainage biomembrane |
| CN109012691A (en) * | 2018-09-19 | 2018-12-18 | 江西萍乡市成宇陶瓷有限责任公司 | A kind of preparation method of energy-saving and environment-friendly efficient ozone catalyst |
| CN109107582A (en) * | 2018-09-19 | 2019-01-01 | 江西萍乡市成宇陶瓷有限责任公司 | A kind of preparation method of efficient ozone catalyst |
| CN109126838A (en) * | 2018-09-19 | 2019-01-04 | 江西萍乡市成宇陶瓷有限责任公司 | A kind of preparation method of ozone catalyst |
| CN109939695A (en) * | 2019-04-03 | 2019-06-28 | 宁夏大学 | A kind of support type O3The preparation of catalyst and its application in coal chemical industry high-salt wastewater COD removal |
| CN110860305A (en) * | 2019-11-22 | 2020-03-06 | 萍乡拓步环保科技有限公司 | Alumina ceramic matrix ozone catalyst and preparation method thereof |
| WO2021196522A1 (en) * | 2020-03-30 | 2021-10-07 | 中国环境科学研究院 | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and preparation method therefor |
| CN113893865A (en) * | 2021-11-17 | 2022-01-07 | 扬州优境环境工程有限公司 | Preparation method of catalyst for ozone oxidation of industrial wastewater |
| CN114471585A (en) * | 2022-02-28 | 2022-05-13 | 山东华特环保科技有限公司 | Ozone catalyst with acetate as precursor and preparation method and application thereof |
| CN115155609A (en) * | 2022-06-22 | 2022-10-11 | 广东中膜科技有限公司 | Manganese-doped iron titanate granular ozone catalyst and preparation method and application thereof |
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Cited By (20)
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|---|---|---|---|---|
| CN104923238A (en) * | 2015-05-25 | 2015-09-23 | 北京铸盟科技有限公司 | Oxidization catalyst used for advanced oxidation, preparation method thereof and application thereof |
| CN105396549A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Preparation method for adsorption material used for treating dye waste water |
| CN105498754A (en) * | 2015-12-23 | 2016-04-20 | 北京碧水源膜科技有限公司 | Catalyst for catalytic oxidation of ozone and preparation method of catalyst |
| CN105838828A (en) * | 2016-05-26 | 2016-08-10 | 许婷 | Leather working treating agent and preparation method thereof |
| CN106040252A (en) * | 2016-05-26 | 2016-10-26 | 格丰环保科技有限公司 | Method for preparing ozone oxidation catalyst |
| CN106799226A (en) * | 2017-01-05 | 2017-06-06 | 杭州绿色环保技术开发有限公司 | A kind of catalyst of ozone oxidation organic matter and preparation method thereof |
| CN106902812A (en) * | 2017-03-14 | 2017-06-30 | 南京大学 | A kind of preparation method of the loaded catalyst for heterogeneous catalysis ozonisation |
| CN106902812B (en) * | 2017-03-14 | 2019-04-19 | 南京大学 | A kind of preparation method of the loaded catalyst for heterogeneous catalysis ozonisation |
| CN108585371A (en) * | 2018-05-18 | 2018-09-28 | 河南海天水务工程有限公司 | A kind of sewerage integrated treatment process of drainage biomembrane |
| CN109126838A (en) * | 2018-09-19 | 2019-01-04 | 江西萍乡市成宇陶瓷有限责任公司 | A kind of preparation method of ozone catalyst |
| CN109107582A (en) * | 2018-09-19 | 2019-01-01 | 江西萍乡市成宇陶瓷有限责任公司 | A kind of preparation method of efficient ozone catalyst |
| CN109012691A (en) * | 2018-09-19 | 2018-12-18 | 江西萍乡市成宇陶瓷有限责任公司 | A kind of preparation method of energy-saving and environment-friendly efficient ozone catalyst |
| CN109939695A (en) * | 2019-04-03 | 2019-06-28 | 宁夏大学 | A kind of support type O3The preparation of catalyst and its application in coal chemical industry high-salt wastewater COD removal |
| CN110860305A (en) * | 2019-11-22 | 2020-03-06 | 萍乡拓步环保科技有限公司 | Alumina ceramic matrix ozone catalyst and preparation method thereof |
| WO2021196522A1 (en) * | 2020-03-30 | 2021-10-07 | 中国环境科学研究院 | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and preparation method therefor |
| US11666892B2 (en) | 2020-03-30 | 2023-06-06 | Chinese Research Academy Of Environment Sciences | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and method for preparing same |
| CN113893865A (en) * | 2021-11-17 | 2022-01-07 | 扬州优境环境工程有限公司 | Preparation method of catalyst for ozone oxidation of industrial wastewater |
| CN114471585A (en) * | 2022-02-28 | 2022-05-13 | 山东华特环保科技有限公司 | Ozone catalyst with acetate as precursor and preparation method and application thereof |
| CN115155609A (en) * | 2022-06-22 | 2022-10-11 | 广东中膜科技有限公司 | Manganese-doped iron titanate granular ozone catalyst and preparation method and application thereof |
| CN115155609B (en) * | 2022-06-22 | 2024-03-01 | 广东中膜科技有限公司 | Manganese-doped ferric titanate granular ozone catalyst and preparation method and application thereof |
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